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K Rissanen

Publications and source records attributed to K Rissanen.

At least 19 recordsLinked to original sources
PubMed2006

An electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric study of the gas-phase stabilities and fragmentation of N-alkylammonium resorcarenes.

Five N-alkylated ammonium resorcarene derivatives, differing either in the nitrogen atom or in the lower rim alkyl chain, were studied using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The main purpose was to clarify the fragmentation and the relative stabilities of the protonated molecules by collision-induced dissociation (CID) experiments. The results indicate that fragmentation of the upper rim alkyl amino substituents at the 2-position occurs readily. Variation in the gas-phase stabilities of these molecules was also observed. In addition, the proposed fragmentation pathways are depicted.

Alkylation↗
PubMed2002

Radioactive contamination in the Arctic--sources, dose assessment and potential risks.

Arctic residents, whose diets comprise a large proportion of traditional terrestrial and freshwater foodstuffs, have received the highest radiation exposures to artificial radionuclides in the Arctic. Doses to members of both the average population and selected indigenous population groups in the Arctic depend on the rates of consumption of locally-derived terrestrial and freshwater foodstuffs, including reindeer/caribou meat, freshwater fish, goat cheese, berries, mushrooms and lamb. The vulnerability of arctic populations, especially indigenous peoples, to radiocaesium deposition is much greater than for temperate populations due to the importance of terrestrial, semi-natural exposure pathways where there is high radiocaesium transfer and a long ecological half-life for this radionuclide. In contrast, arctic residents with diets largely comprising marine foodstuffs have received comparatively low radiation exposures because of the lower levels of contamination of marine organisms. Using arctic-specific information, the predicted collective dose is five times higher than that estimated by UNSCEAR for temperate areas. The greatest threats to human health and the environment posed by human and industrial activities in the Arctic are associated with the potential for accidents in the civilian and military nuclear sectors. Of most concern are the consequences of potential accidents in nuclear power plant reactors, during the handling and storage of nuclear weapons, in the decommissioning of nuclear submarines and in the disposal of spent nuclear fuel from vessels. It is important to foster a close association between risk assessment and practical programmes for the purposes of improving monitoring, formulating response strategies and implementing action plans.

Agaricales↗
PubMed2001

Partial aminomethylation of resorcarenes.

Aminomethylation of resorcarenes at the wider rim with bulky diisopropylamine and formaline leads to trisubstituted derivatives. Analogous reaction with C(2v)-symmetrical resorcarene tetratosylate gives the monoaminomethylated compound. Further reactions of remaining unsubstituted resorcinol rings result in new resorcarene derivatives. [reaction: see text]

Journal Article↗
PubMed2001

Synthesis, characterization and the first crystal structure of the Zn(II) complex of 4,6-O-ethylidine-N-(2-hydroxybenzylidene)-beta-D-glucopyranosylamine.

4,6-O-Ethylidine-N-(2-hydroxybenzylidene)-beta-D-glucopyranosylamine (H(3)L(1)) and N-(5-bromo-2-hydroxybenzylidene-4,6-O-ethylidine-beta-D-glucopyranosylamine (H(3)L(2)) molecules possessing a single bond C-1 single bond N double bond C(H) single bond moiety for metal-ion binding were synthesized by condensing the 4,6-O-ethylidene-beta-D-glucopyranosylamine with salicylaldehyde or 5-bromosalicylaldehyde. Complexes of these ligands with Zn(II) were isolated and characterized using elemental analysis, FTIR, UV-Vis absorption, NMR spectroscopic and FAB mass spectrometric techniques. The structure of the Zn(II) complex derived from H(3)L(1) was established for the first time by a single-crystal X-ray diffraction study. The anomeric nature of the saccharide moiety was established based on (1)H NMR studies and was confirmed by the crystal structure. Further, the structure and binding aspects of the ligand, and the coordination features of this in its Zn(II) complex were derived from the corresponding crystal structure.

Crystallography, X-Ray↗
PubMed2001

Synthesis, characterisation and crystal structures of Schiff bases from the reaction of 4,6-O-ethylidene-beta-D-glucopyranosylamine with substituted salicylaldehydes.

Multiple chemical modifications were carried out on D-glucose to result in the corresponding Schiff bases. Such modifications performed on D-glucose not only helped in increasing the solubility of the products in nonaqueous solvents, but also restricted the anomerisation of the saccharide moiety in solution. NMR study of the products revealed the presence of the beta-anomeric form of the saccharide moiety in Me(2)SO solution. All the compounds were characterised by analytical and spectral methods. The literature is devoid of any crystal structures of saccharide-Schiff base combinations of the type reported in this paper. The crystal structures of these molecules exhibited a tridentate, ONO binding core. These studies further revealed that the compounds in the solid state were in the beta-D-pyranose form with the (4)C(1) chair conformation. The compounds exhibited interesting lattice structures assisted through weak interactions of the type O-H...O and C-H...O. The lattice structure of one of these compounds exhibited channels filled with chloroform molecules.

Aldehydes↗
PubMed2001

Dominant/recessive behavior in the expression of molecular information: self-assembly of inorganic macrocyclic architectures containing coordinatively unsaturated ligands.

The polytopic ligand 1 contains three different metal ion binding subunits forming two substructures that code for the self-assembly of two different coordination structures (helicate and grid type) under metal ion complexation. Reaction with Cu(II) and Zn(II) ions generates the coordinatively unsaturated architectures 8 and 9 resulting from the formation of two double helicate arrangements. Their crystal structure has been determined by x-ray diffraction. These results show that the double helical motif is expressed at the expense of the grid type one, indicating the dominant/recessive behavior of the system. Together with earlier studies on the linear combination and crossover processing schemes, the dominant/recessive generation of 8 and 9 completes the demonstration of principle of the modes of multiple expression of molecular information in a multicode programmed chemical system.

Journal Article↗
PubMed2001

Self-assembly and anion encapsulation properties of cavitand-based coordination cages.

Two novel classes of cavitand-based coordination cages 7a--j and 8a--d have been synthesized via self-assembly procedures. The main factors controlling cage self-assembly (CSA) have been identified in (i) a P--M--P angle close to 90 degrees between the chelating ligand and the metal precursor, (ii) Pd and Pt as metal centers, (iii) a weakly coordinated counterion, and (iv) preorganization of the tetradentate cavitand ligand. Calorimetric measurements and dynamic (1)H and (19)F NMR experiments indicated that CSA is entropy driven. The temperature range of the equilibrium cage-oligomers is determined by the level of preorganization of the cavitand component. The crystal structure of cage 7d revealed the presence of a single triflate anion encapsulated. Guest competition experiments revealed that the encapsulation preference of cages 7b,d follows the order BF(4)(-) > CF(3)SO(3)(-) >> PF(6)(-) at 300 K. ES-MS experiments coupled to molecular modeling provided a rationale for the observed encapsulation selectivities. The basic selectivity pattern, which follows the solvation enthalpy of the guests, is altered by size and shape of the cavity, allowing the entrance of an ancillary solvent molecule only in the case of BF(4)(-).

Journal Article↗
PubMed2001

Resorcarenes in the boat conformation as building blocks for hydrogen-bonded assemblies including two ammonium cations.

Crystal structures are reported for various co-crystals of rccc-resorcarenes with triethylammonium chloride. Usually, two molecules of a C2v-symmetric tetraester 2 in the boat conformation are linked through four hydrogen-bonded chloride anions to give dimeric assemblies. Two of the chloride anions may be replaced by four hydrogen-bonded ethanol molecules in an otherwise similar structure. These assemblies, which consist of six or eight components, posses voluminous, negatively charged chambers in which two triethylammionium cations, 3+, are included as guests by strong electrostatic and hydrogen-bonding interactions. The host-guest N-H...Cl hydrogen bonds were clearly detected at 173 K. These are the first examples of hydrogen-bonded, solid-state capsules trapping two ions of the same charge in close proximity. In the 1:2 complex with 3+ Cl-, the molecule of the parent resorcarene 1 also adopts a boat conformation whose cavity is considerably extended by four hydrogen-bonded chloride anions. The pocket formed in this way again includes two 3+ ions as a result of electrostatic and hydrogen bonding host-guest interactions. All these structures show that the boat conformers of resorcarenes can be used as a novel motif for the construction of hydrogen-bonded assemblies capable of molecular inclusion and encapsulation.

Journal Article↗
PubMed2001

Mass spectrometric studies on small open-chain piperazine-containing ligands and their transition metal complexes.

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry was used to characterize the complexes formed between open-chain piperazine-containing ligands and transition metal salts (Cobalt, Copper, Zinc, and Cadmium as chlorides, nitrates, and acetates). Only single-charged complexes were observed, formed of one ligand (L) and mainly one metal ion (M). Since the net charge of the complexes was one, a counterion (X) was attached to some of the complexes, with formation of [L + M + X]+ complexes, and a proton was lost from others, as in [L - H + M]+ complexes. In most cases the composition of the complexes was more dependent on the ligand than the metal salt. Collision-induced dissociation measurements showed that complexes with related composition often differed in structure, or that interactions between the ligand and the metal ion were not alike. The metal ion influenced considerably the fragmentation pathways of the ligands, so that the fragmentation products could be used to deduce the binding sites of the metal. The variations observed in fragmentation behavior of complexes possessing the same ligand but different metal ions can mostly be explained by the ionic radius and electronic configuration of the metal ion. The results indicated a preference of the piperazine ring of the coordinated ligand for the boat conformation.

Cobalt↗
PubMed2001

Mass spectrometric studies on pyridine-piperazine-containing ligands and their complexes with transition metals formed in solution.

Electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) methods were used to study open-chain piperazine-containing ligands (L) and their complexes formed with transition-metal salts. ESI and MALDI measurements were performed with a Fourier transform ion cyclotron resonance (FT-ICR) and a time-of-flight (TOF) mass spectrometer, respectively. Only singly charged complexes, between one ligand and one or several metal ions, were formed in the ESI measurements. Because the net charge was always one, one or several counterions were attached to the complex. Under ESI conditions, the complexes formed between the ligands and metal (Co, Ni, Cu, and Cd) salts were [L + M + X](+), [L + H + M + X(2)](+) and [L + M(2) + X(3)](+) (M = metal ion, X = counterion). In collision induced dissociation reactions the [L + H + M + X(2)](+) complexes easily eliminated one proton and one counterion. Fragmentation pathways were more dependent on the metal ion than the ligand, and elimination of the second counterion occurred with one proton from copper and nickel complexes and with one proton and one hydrogen from cobalt complexes. Differences in the fragmentation of the complexes could be due to electronic configuration of the metal ion. In the MALDI measurements the ratio between the [L + H](+) and [L - H](+) ions varied with the matrix. Fragmentation of the ligands through elimination of 2-methylpyridine end groups occurred with the aromatic matrices containing carboxylic acid and hydroxyl substituents. Ionization of the complexes was not successful with MALDI as the matrix molecules were also attached to the complexes.

Journal Article↗
PubMed2001

Effect of chemical pollution on forms of 137Cs, 90Sr and 239,240Pu in arctic soil studied by sequential extraction.

The aim of the present study was to determine the forms of 137Cs, 90Sr and 239,240Pu occurring in different soil horizons using sequential extraction of samples taken from four sites located along a pollution gradient from the copper-nickel smelter at Monchegorsk in the Kola Peninsula, Russia, and from a reference site in Finnish Lapland in 1997. A selective sequential-leaching procedure was employed using a modification of the method of Tessier, Cambell and Bisson ((1979). Analytical Chemistry, 51, 844-851). For 137Cs the organic (O) and uppermost mineral (E1) layer were studied, for 90Sr and 239,240Pu only the uppermost organic layer (Of). The fraction of 137Cs occurring in readily exchangeable form in the organic layer was about 50% at the reference site and decreased as a function of pollution, being 15% at the most polluted site in the Kola Peninsula. There was a clear positive correlation in the O layer between the distance from the smelter and the percentage of 137Cs extracted in the readily exchangeable fraction (Spearman correlation rsp = 0.7805, p = 0.0001), whereas in the E1 layer no correlation was evident. The distribution of 90Sr in the Of layer was similar at all sites, with the highest amounts occurring in exchangeable form and bound to organic matter, whereas stable Sr showed a somewhat different distribution with the highest amount in the oxide fraction. Most of the 239,240Pu was bound to organic matter. Chemical pollution affected the exchangeable fraction of 239,240Pu, which was about 1% at the most polluted site and 4-6% at the other sites.

Arctic Regions↗
PubMed2001

Analysis of radioactive particles from the Kola Bay area.

Two types of radioactive particle were identified in marine sediment and lichen samples collected from the Kola Bay, NW Russia. The particles were identified by means of gamma-ray spectrometry and autoradiography, separated and subjected to various analysis techniques. Several complementary techniques are needed to characterise particle properties thoroughly. 137Cs was present in the sediment matrix in large (approximately 100 microns) greenish particles that were most probably pieces of paint. Although their element composition was heterogeneous, 137Cs was found to be evenly distributed. 60Co in the lichen matrix was present in small (approximately 1 micron) particles. No U or transuranium elements were detected in either type of particle.

Autoradiography↗
PubMed2000

Recognition-directed supramolecular assemblies of metal complexes of terpyridine derived ligands with self-complementary hydrogen bonding sites.

The synthesis and X-ray structures of three metal complexes with terpyridine-derived ligands that contain amino-pyrimidine and amino-pyrazine moieties are presented. They have been designed in view of directing their self-assembly into specific supramolecular arrays through molecular recognition interactions. The solid-state structures indeed reveal extensive hydrogen-bonded networks. The Co complex 4a with PF6- counterions builds a two-dimensional infinite interwoven grid through strong double hydrogen bonds (d(N-H-N) =2.918-3.018 A) between the amino groups and the N atoms of the rings, with all H-bonding sites saturated. Changing the anions to BF4- in 4b leads to a similar infinite but partially broken grid with a quarter of the H-bonding sites unsaturated (d(N-H-N)=2.984-3.206 A). In the case of the Zn complex 12 with triflate anions, half of the hydrogen bonds are formed. Only one of the two orthogonal ligands has hydrogen bonds (d(N-H-N) = 3.082, 3.096 A) to the neighbouring complexes and thus builds linear, supramolecular, polymeric chains. These structural differences are mainly attributed to crystal-packing effects caused by the different anions. The data presented here may also be regarded as a prototype for the generation of organised arrays through sequential self-assembly processes.

Journal Article↗
PubMed2000

Hydrogen-bonding effects in calix

The synthesis and spectroscopic characterization of self-assembling calix[4]arene based capsules 1a.1a and 1b.1b are described. These compounds feature four urea substituents at the upper rims and four secondary amide fragments at the lower rims that can participate in inter- and intramolecular hydrogen bonding in apolar solution. Communication between the calixarene rims in 1a, b influences the self-assembled cavity's size and shape. Specifically. dimerization results in a perfect cone conformation of the calixarene skeleton in 1a, b and stabilizes a seam of intramolecular amide C=O...H-N hydrogen bonds at the lower rim. This seam is cycloenantiomeric, with either clockwise or counterclockwise arrangements of the head-to-tail amides. Complexation of Na+-cation breaks hydrogen bonds at the lower rim but maintains the capsular assembly. Encapsulation properties of 1a.1a and 1b.1b were studied in nonpolar solvents and their binary mixtures as well as through heterodimerization experiments. The presence of amide groups at the lower rim causes notable differences in the capsule's binding affinities when compared to the corresponding tetraester capsules 1c.1c and 1d.1d. In the monomeric state calixarenes 1a, b are in a pinched cone conformation. The solid state X-ray crystallographic studies with monomeric 1a reveal only two intramolecular C=O...H-N hydrogen bonds between the adjacent amides at the lower rim, and an extensive network of intermolecular hydrogen bonds between urea groups at the upper rim.

Journal Article↗
PubMed2000

Induced-fit molecular recognition with water-soluble cavitands

Synthesis of novel water-soluble cavitands 1 and 2 and their complexes--the caviplexes--is described. The solubility in water derives from four primary ammonium groups on the lower rim and eight secondary amide groups on the upper rim. Cavitands 1 and 2 exist as D2d velcraplex dimers in aqueous solution but the addition of lipophilic guests 15-24 induces conformational changes to the vase-like structures. The internal cavity dimensions are 8 x 10 A, and the exchange rates of guests in the caviplexes are slow on the NMR time-scale (room temperature and 600 MHz). The direct observation of bound species and the stoichiometry of the complexes is reported. The association constants (Ka) between 0.4 x 10(-1) (-deltaG295= 0.7 kcalmol(-1)) and 1.4 x 10(2)M(-1) (-deltaG295=2.9 kcalmol(-1)) in D2O and 1.4 x 10(1)(-deltaG295= 1.7 kcalmol(-1)) and 2.8 x 10(4)M(-1)(-deltaG295=6.0 kcalmol(-1)) in [D4]methanol for aliphatic guests 16-24 were determined. Guest exchange rates of the new hosts 1 and 2 are considerably slower than rates observed for typical open-ended cavities in aqueous solution.

Journal Article↗
PubMed1999

Soil to plant uptake of fallout 137Cs by plants from boreal areas polluted by industrial emissions from smelters.

To study the impact of industrial pollution on the soil-to-plant uptake of fallout-radiocesium in a boreal forest ecosystem, four study sites were selected at distances of 7, 16, 21 and 28 km from the large copper-nickel smelter at Monchegorsk on the Kola Peninsula (Russia). At each site, soil and selected plant species were sampled from five plots and analysed separately for 137Cs and 40K. The data show that the root-uptake of 137Cs, as characterised by the median aggregated transfer-factor T(ag), decreased significantly (P < 0.05) with decreasing distance from the smelter for the plants Vaccinium myrtillus (from 0.023 to 0.007 m2 kg-1) and Empetrum nigrum (from 0.015 to 0.007 m2 kg-1), but increased for Deschampsia flexuosa (from 0.013 to 0.031 m2 kg-1). For Vaccinium vitis-idaea a significant trend for the T(ag) was not observed. The median 40K activity concentrations in these plants also decreased significantly (P < 0.001) with decreasing distance from the smelter for Vaccinium myrtillus (from approx. 140 to 20 Bq kg-1 dry wt.), Empetrum nigrum (from approx. 90 to 40 Bq kg-1 dry wt.), and also for Deschampsia flexuosa (from approx. 270 to 40 Bq kg-1 dry wt.). For Vaccinium vitis-idaea such a continuous significant trend was not observed. The results for the Cu-Ni polluted soils thus show: (1) that the soil-to-plant transfer of radiocesium can be significantly modified; (2) that these modifications are quite specific; and (3) that modifications of the uptake of potassium do not always correspond to those of radiocesium.

Biological Transport, Active↗